CN111836844A - Copolymer fibers and related methods and articles - Google Patents

Copolymer fibers and related methods and articles Download PDF

Info

Publication number
CN111836844A
CN111836844A CN201980018520.6A CN201980018520A CN111836844A CN 111836844 A CN111836844 A CN 111836844A CN 201980018520 A CN201980018520 A CN 201980018520A CN 111836844 A CN111836844 A CN 111836844A
Authority
CN
China
Prior art keywords
mol
units
fiber
polysiloxane
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201980018520.6A
Other languages
Chinese (zh)
Inventor
孙成均
杰罗尔德·詹姆斯·哈丁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
SABIC Global Technologies BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of CN111836844A publication Critical patent/CN111836844A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Copolymer fibers are prepared from a composition that includes specific amounts of a block polyestercarbonate-polysiloxane and a flame retardant. The fibers have an equivalent circular diameter of 10-60 microns. Methods of forming the fibers are also described, as are various articles comprising the fibers, including woven, knitted, and nonwoven fabrics.

Description

Copolymer fibers and related methods and articles
Background
Polyestercarbonate-polysiloxanes are copolymers that exhibit a desirable balance of flame retardancy and ductility. Heretofore, such copolymers and compositions thereof have been used primarily in injection molding, sheet extrusion, and additive manufacturing applications. Polyestercarbonate-polysiloxanes have been used in fiber production. See, for example, U.S. patent application publication No. US 2013/0260088A1 to David et al. However, there remains a need for polyestercarbonate-polysiloxane compositions that exhibit more robust (robust) processing characteristics for fiber melt spinning.
Disclosure of Invention
One embodiment is a copolymer fiber: wherein the copolymeric fiber comprises a composition comprising 90 wt% to 98 wt%, based on the total weight of the composition, of a block polyestercarbonate-polysiloxane comprising a polyester block comprising resorcinol ester units having the structure:
Figure BDA0002675963860000011
polycarbonate blocks comprising carbonate units having the structure
Figure BDA0002675963860000012
Wherein R is1At least 60% of the total number of groups are aromatic divalent groups, and polysiloxane blocks containing dimethylsiloxane units; wherein the block polyestercarbonate-polysiloxane comprises 30 mol% to 90 mol% resorcinol ester units, 5 mol% to 35 mol% carbonate units, based on the total moles of carbonate and ester units, wherein R1Is 1, 3-phenylene, and from 5 mol% to 35 mol% of carbonate units, where R1Is that
Figure BDA0002675963860000021
And further comprising 0.2 wt% to 4 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane; 2-10 wt% of a flame retardant; wherein the fibers have an equivalent circular diameter (equivalent circular diameter) of 10-60 microns.
Another embodiment is a method of forming a fiber, the method comprising: melt spinning (melt spinning) the composition to form a fiber; and wherein the composition comprises 90 wt% to 98 wt%, based on the total weight of the composition, of a block polyestercarbonate-polysiloxane comprising polyester blocks comprising resorcinol ester units having the following structure:
Figure BDA0002675963860000022
polycarbonate blocks comprising carbonate units having the structure
Figure BDA0002675963860000023
Wherein R is1At least 60% of the total number of groups are aromatic divalent groups, and polysiloxane blocks containing dimethylsiloxane units; wherein the block polyestercarbonate-polysiloxane comprises 30 mol% to 90 mol% resorcinol ester units, 5 mol% to 35 mol% carbonate units, based on the total moles of carbonate and ester units, wherein R1Is 1, 3-phenylene, and from 5 mol% to 35 mol% of carbonate units, where R is1Is that
Figure BDA0002675963860000031
And further comprising 0.2 wt% to 4 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane; 2-10 wt% of a flame retardant; and wherein the fibers have an equivalent circular diameter of 10-60 microns.
Another embodiment is an article comprising the fiber.
These and other embodiments are described in detail below.
Drawings
The figure is a schematic diagram of a melt spinning apparatus (melt spinning apparatus).
Detailed Description
The present inventors have determined that melt spun fibers prepared from compositions comprising specific amounts of a block polyestercarbonate-polysiloxane and a flame retardant exhibit the more robust (robust) processing characteristics of fiber melt spinning, reduced hot air shrinkage and reduced heat release rate.
Thus, one embodiment is a multipolymer fiber wherein the multipolymer fiber comprises a composition comprising from 90 wt% to 98 wt%, based on the total weight of the composition, of a block polyestercarbonate-polysiloxane comprising polyester blocks comprising resorcinol ester units having the structure
Figure BDA0002675963860000041
Polycarbonate blocks comprising carbonate units having the structure
Figure BDA0002675963860000042
Wherein R is1At least 60% of the total number of groups are aromatic divalent groups, and polysiloxane blocks containing dimethylsiloxane units; wherein the block polyestercarbonate-polysiloxane comprises 30 mol% to 90 mol% resorcinol ester units, 5 mol% to 35 mol% carbonate units, based on the total moles of carbonate and ester units, wherein R1Is 1, 3-phenylene, and from 5 mol% to 35 mol% of carbonate units, where R is1Is that
Figure BDA0002675963860000043
And based on the block polyestercarbonate-polysilicones(ii) a weight of siloxane, further comprising 0.2 wt% to 4 wt% of dimethylsiloxane units; 2-10 wt% of a flame retardant; wherein the fibers have an equivalent circular diameter of 10-60 microns.
The copolymeric fibers are prepared from a composition comprising a block polyestercarbonate-polysiloxane. The block polyestercarbonate-polysiloxane is a copolymer comprising at least one polyester block, at least one polycarbonate block and at least one polysiloxane block. Specifically, the at least one polyester block comprises resorcinol ester units, each resorcinol ester unit having the structure
Figure BDA0002675963860000051
The at least one polycarbonate block comprises carbonate units, each carbonate unit having the structure
Figure BDA0002675963860000052
Wherein R is1At least 60% of the total number of groups are aromatic divalent groups and the at least one polysiloxane block comprises dimethylsiloxane units.
In some embodiments, the aromatic divalent group is C6-C24An aromatic divalent group. When not all R1When the radicals are all aromatic, the remainder are C2-C24An aliphatic divalent group. In some embodiments, each R is1Is a group of the formula:
Figure BDA0002675963860000053
wherein A is1And A2Each independently is a monocyclic divalent aryl radical, and Y1Is provided with one or two groups A1And A2A bridging group of spaced apart atoms. A. the1And A2Examples of (B) include 1, 3-phenylene and 1, 4-phenylene, each optionally substituted with one, two or three C1-C6Alkyl substitution. The bridging group Y1Can be C1-C12(divalent) alkylene group. As used herein, the term "hydrocarbyl", whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen, unless explicitly identified as "substituted hydrocarbyl". The hydrocarbyl residue can be aliphatic or aromatic, straight chain, cyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. When the hydrocarbyl residue is described as substituted, it can contain heteroatoms over and above carbon and hydrogen. In some embodiments, one atom will be a1And A2And (4) separating. Y is1Illustrative examples of radicals are-O-, -S-, -S (O) -, -S (O)2-, -C (O) -, methylene (-CH)2-; also known as methylidene), ethylidene (-CH (CH)3) -) isopropylidene (-COOR-), C (-CH (CH)3)2-), neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, adamantylidene, cyclohexylidene methylene, cyclohexylmethylene and 2- [2.2.1]-bicycloheptylidene.
In some embodiments, the resorcinol ester units comprise resorcinol isophthalate/terephthalate units and the carbonate units comprise resorcinol carbonate units and bisphenol-a carbonate units.
The block polyestercarbonate-polysiloxane comprises 30 mol% to 90 mol% resorcinol ester units, 5 mol% to 35 mol% carbonate units, based on the total moles of carbonate and ester units, wherein R1Is 1, 3-phenylene (i.e., the carbonate unit is a resorcinol carbonate unit), and from 5 mol% to 35 mol% of carbonate units, wherein R is1Is that
Figure BDA0002675963860000061
(i.e., the carbonate units are bisphenol A carbonate units). In the range of 30 mol% to 90 mol%, the resorcinol ester units can be in an amount of 50 mol% to 90 mol%, or 70 mol% to 90 mol%. In the range of 5 mol% to 35 mol%, the amount of resorcinol carbonate units can be 5 mol% to 25 mol%, or 5 mol% to 15 mol%. In the range of 5 mol% to 35 mol%, the amount of bisphenol a carbonate units can be 5 mol% to 25 mol%, or 5 mol% to 15 mol%. The block polyestercarbonate-polysiloxane further comprises 0.2 wt% to 4 wt% dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane. Within this range, the amount of dimethylsiloxane units can be 0.4 wt% to 2 wt%, or 0.5 wt% to 2 wt%.
In a very specific embodiment, the block polyestercarbonate-polysiloxane comprises resorcinol isophthalate/terephthalate units in an amount of 70 mol% to 90 mol%, resorcinol carbonate units in an amount of 5 mol% to 15 mol%, and bisphenol a carbonate units in an amount of 5 mol% to 15 mol%, based on the total moles of carbonate and ester units, and further comprises dimethylsiloxane units in an amount of 0.5 wt% to 2 wt%, based on the total weight of the block polyestercarbonate-polysiloxane.
There is no particular limitation on the structure of the end groups on the block polyestercarbonate-polysiloxane. A capping agent (also referred to as a chain stopper or chain terminator) can be included during polymerization to provide end groups. Examples of the blocking agent include monocyclic phenols such as phenol, p-cyanophenol, and C1-C22Alkyl-substituted phenols such as p-cumylphenol, resorcinol monobenzoate, and p-tert-butylphenol; monoethers of dihydric phenols, such as p-methoxyphenol; monoesters of bisphenols, such as resorcinol monobenzoate; functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryloyl chloride; monochloroformates, such as phenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumyl phenyl chloroformate and toluene chloroformate. Combinations of different end groups can be used. In some embodiments, the block polyestercarbonate-polysiloxane has a weight average molecular weight of 15,000-55,000 g/mole, as determined by gel permeation chromatography using polycarbonate standards. Within this range, the weight average molecular weight can be 18,000-50,000 g/mole.
Methods for preparing block polyestercarbonate-polysiloxanes are known and are described, for example, in U.S. Pat. No. 7,790,292B2 to Colborn et al.
The composition comprises 90 wt% to 98 wt% of a block polyestercarbonate-polysiloxane, based on the total weight of the composition. Within this range, the amount of the block polyestercarbonate-polysiloxane can be 90 wt% to 97 wt%, or 91 wt% to 96 wt%.
In addition to the block polyestercarbonate-polysiloxane, the composition also contains a flame retardant. Flame retardants are chemical compounds or mixtures of chemical compounds that can improve the flame retardancy of thermoplastic compositions. Suitable flame retardants include organic phosphate esters, metal dialkylphosphinate salts, melamine-containing flame retardants, and combinations thereof.
In some embodiments, the flame retardant comprises an organophosphate ester. Exemplary organophosphate ester flame retardants include phosphate esters comprising phenyl groups, substituted phenyl groups, or a combination of phenyl and substituted phenyl groups, resorcinol-based bisaryl phosphate esters such as, for example, resorcinol bis (diphenyl phosphate), and bisphenol-based ones such as, for example, bisphenol a bis (diphenyl phosphate). In some embodiments, the organic phosphate is selected from the group consisting of tris (alkylphenyl) phosphate (e.g., CAS registry No. 89492-23-9 or CAS registry No. 78-33-1), resorcinol bis (diphenyl phosphate) (CAS registry No. 57583-54-7), bisphenol a bis (diphenyl phosphate) (CAS registry No. 181028-79-5), triphenyl phosphate (CAS registry No. 115-86-6), tris (isopropylphenyl) phosphate (e.g., CAS registry No. 68937-41-7), tert-butylphenyl diphenyl phosphate (CAS registry No. 56803-37-3), bis (tert-butylphenyl) phenyl phosphate (CAS registry No. 65652-41-7), tris (tert-butylphenyl) phosphate (CAS registry No. 78-33-1), and combinations thereof. In some embodiments, the flame retardant does not include brominated polycarbonate. In some embodiments, the flame retardant is halogen-free. In some embodiments, the organophosphate ester comprises an oligomeric phosphate ester, which can be a halogen-free oligomeric phosphate ester.
In some embodiments, the flame retardant comprises a metal dialkylphosphinate. As used herein, the term "metal dialkylphosphinate" refers to a salt comprising at least one metal cation and at least one dialkylphosphinate anion. In some embodiments, the metal dialkylphosphinate has the formula:
Figure BDA0002675963860000081
wherein R isaAnd RbEach independently is C1-C6An alkyl group; m is calcium, magnesium, aluminum or zinc; and d is 2 or 3. RaAnd RbExamples of (b) include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and n-pentyl. In some embodiments, RaAnd RbIs ethyl, M is aluminum, and d is 3 (i.e., the metal dialkylphosphinate is aluminum tris (diethylphosphinate)).
In some embodiments, the flame retardant comprises a melamine-containing flame retardant. Melamine-containing flame retardants include those comprising a melamine-containing base and a phosphate or pyrophosphate or polyphosphate or cyanuric acid. In some embodiments, the melamine-containing flame retardant has the formula
Figure BDA0002675963860000091
Wherein g is 1-10,000 and the ratio of f to g is 0.5:1-1.7:1, specifically 0.7:1-1.3:1, more specifically 0.9:1-1.1: 1. It is to be understood that the formula includes species in which one or more protons are transferred from the phosphate group to the melamine group. When g is 1, the melamine containing flame retardant is melamine phosphate (CAS registry number 20208-95-1). When g is 2, the melamine containing flame retardant is melamine pyrophosphate (CAS registry number 15541-60-3). When g averages greater than 2, the melamine containing flame retardant is melamine polyphosphate (CAS registry number 56386-64-2). In some embodiments, the melamine-containing flame retardant is melamine pyrophosphate, melamine polyphosphate, or a mixture thereof. In some embodiments wherein the melamine containing flame retardant is a melamine polyphosphate, g has an average value of greater than 2 to 10,000, specifically 5 to 1,000, more specifically 10 to 500. In some embodiments wherein the melamine containing flame retardant is a melamine polyphosphate flame retardant, g has an average value of greater than 2 to 500. Methods for preparing melamine phosphate, melamine pyrophosphate and melamine polyphosphate are known in the art and are all commercially available. For example, melamine polyphosphate can be prepared by reacting polyphosphoric acid and melamine, as described, for example, in U.S. Pat. No.6,025,419 to Kasowski et al, or by heating melamine pyrophosphate to constant weight at 290 ℃ under nitrogen, as described in U.S. Pat. No.6,015,510 to Jacobson et al. In some embodiments, the melamine-containing flame retardant comprises melamine cyanurate.
The composition comprises a flame retardant in an amount of 2 wt% to 10 wt%, based on the total weight of the composition. Within this range, the flame retardant amount can be about 3 wt% to 10 wt%, or 4 wt% to 9 wt%.
The composition can optionally further comprise one or more additives known in the thermoplastics art. Suitable additives include, for example, stabilizers, mold release agents, lubricants, processing aids, anti-drip agents, nucleating agents, UV blockers, dyes, pigments, antioxidants, antistatic agents, blowing agents, mineral oils, metal deactivators, antiblocking agents (antiblocking agents), and combinations thereof. When present, such additives are generally used in a total amount of less than or equal to 2 wt%, based on the total weight of the composition. In some embodiments, the additive is used in an amount less than or equal to 1 wt%, or less than or equal to 0.5 wt%. In some embodiments, the composition comprises 0 to 1ppm by weight of a colorant. In some embodiments, the composition does not comprise a colorant.
In some embodiments of the fiber, the composition comprises 91 wt% to 96 wt% of the block polyestercarbonate-polysiloxane and 4 wt% to 9 wt% of the flame retardant, based on the total weight of the composition.
In some embodiments of the fiber, the total amount of the block polyestercarbonate-polysiloxane and the flame retardant is 98 wt% to 100 wt%, or 99 wt% to 100 wt%.
In some embodiments of the fiber, the block polyestercarbonate-polysiloxane comprises 70 mol% to 90 mol% resorcinol ester units, 5 mol% to 15 mol% carbonate units, based on the total moles of carbonate and ester units, wherein R is1Is 1, 3-phenylene, and from 5 mol% to 15 mol% of carbonate units, where R is1Is that
Figure BDA0002675963860000111
And further comprises from 0.5 wt% to 2 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane.
In some embodiments, the composition does not include polycarbonate. In some embodiments, the composition does not include a polyester. In some embodiments, the composition does not include a polyestercarbonate. In some embodiments, the composition does not include an impact modifier. In some embodiments, the composition does not include polycarbonate and polyester and polyestercarbonate and an impact modifier.
The fibers have an equivalent circular diameter of 10-60 microns. The equivalent circular diameter of a fiber is the diameter of a circle having the same area as the cross-sectional area of the fiber under consideration. For example, if the fibers considered have an area of 400 μm2The equivalent circular diameter of the fiber is 22.57 microns. In the range of 10-60 microns, the equivalent circle diameter can be 15-50 microns. The shape of the cross-section of the fiber is not particularly limited, and can be, for example, circular or elliptical or triangular or square or rectangular. In some embodiments, the fiber cross-section is circular.
Another embodiment is a method of forming a fiber, the method comprising: melt spinning the composition to form fibers; wherein the composition comprises 90 wt% to 98 wt%, based on the total weight of the composition, of a block polyestercarbonate-polysiloxane comprising polyester blocks comprising resorcinol ester units having the following structure:
Figure BDA0002675963860000112
polycarbonate blocks comprising carbonate units having the structure
Figure BDA0002675963860000121
Wherein R is1At least 60% of the total number of groups are aromatic divalent groups, and polysiloxane blocks containing dimethylsiloxane units; wherein the block polyestercarbonate-polysiloxane comprises 30 mol% to 90 mol% resorcinol ester units, 5 mol% to 35 mol% carbonate units, based on the total moles of carbonate and ester units, wherein R1Is 1, 3-phenylene, and from 5 mol% to 35 mol% of carbonate units, where R is1Is that
Figure BDA0002675963860000122
And further comprising 0.2 wt% to 4 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane; and 2 wt% to 10 wt% of a flame retardant; and wherein the fibers have an equivalent circular diameter of 10-60 microns.
All of the compositional variations described above in the context of the fiber also apply to the method of forming the fiber.
In some embodiments, the melt spinning is characterized by a draw down ratio (draw down ratio) of 280-550, an apparent shear rate of 170-1700s-1And a mechanical draw ratio of 0.95 to 1.2. The draw ratio is unitless and is defined as the ratio of the speed of the melt exiting the spinneret nozzle (spinneret nozzle) in meters/minute to the fiber speed on the first godet roll (godet) in meters/minute. In the range of 280-550, the stretch ratio can be 350-450. Apparent shear rate (in s)-1In units) is defined according to the following formula
Apparent shear Rate(s)-1)＝4Q/πR3ρ
Where Q is the melt throughput (g/sec) per spinneret nozzle, R is the nozzle radius (in centimeters), and p is the polymerizationMelt density (in g/cm)3In units). At 170--1Can be 275-990s-1. The mechanical draw ratio is unitless and is defined as the ratio of the first godet (godet) speed (m/min) to the winder (winder) speed (m/min). Within the range of 0.95-1.2, the mechanical draw ratio can be 0.98-1.1.
Another embodiment is an article comprising the fiber of any of the variations described above. In some embodiments, the article comprises a woven fabric (woven fabric) comprising the fiber. In other embodiments, the article comprises a knit fabric (knit fabric) comprising the fiber. In other embodiments, the article comprises a nonwoven fabric (nonwoven fabric) comprising the fibers. Nonwoven fabrics can be prepared by processes including, for example, wet-laid (wet-laid), dry-laid (dry-laid), air-laid (air-laid), melt-blown (melt-blown), spunbond (spunbond) and spunlace (spunlace).
The present invention includes at least the following aspects.
Aspect 1: a multipolymer fiber, wherein the multipolymer fiber comprises a composition comprising 90 wt% to 98 wt%, based on the total weight of the composition, of a block polyestercarbonate-polysiloxane comprising polyester blocks comprising resorcinol ester units having the structure
Figure BDA0002675963860000131
Polycarbonate blocks comprising carbonate units having the structure
Figure BDA0002675963860000141
Wherein R is1At least 60% of the total number of groups are aromatic divalent groups, and polysiloxane blocks containing dimethylsiloxane units; wherein the block polyestercarbonate-polysiloxane comprises 30 mol% to 90 mol% of m-phenylene bis based on the total moles of carbonate and ester unitsPhenolic ester units, from 5 mol% to 35 mol% of carbonate units wherein R1Is 1, 3-phenylene, and from 5 mol% to 35 mol% of carbonate units in which R is1Is that
Figure BDA0002675963860000142
And further comprising 0.2 wt% to 4 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane; and 2 wt% to 10 wt% of a flame retardant; wherein the fibers have an equivalent circular diameter of 10-60 microns.
Aspect 2: the fiber of aspect 1, wherein the block polyestercarbonate-polysiloxane comprises 0.5 wt% to 2 wt% dimethylsiloxane units.
Aspect 3: the fiber of aspect 1 or 2, wherein the flame retardant comprises an organophosphate ester.
Aspect 4: the fiber of aspect 3, wherein the organophosphate ester comprises an oligomeric phosphate ester.
Aspect 5: the fiber of any of aspects 1-4, wherein the composition comprises 91 wt% to 96 wt% of the block polyestercarbonate-polysiloxane and 4 wt% to 9 wt% of the flame retardant, based on the total weight of the composition.
Aspect 6: the fiber of any of aspects 1-5, wherein the total amount of the block polyestercarbonate-polysiloxane and the flame retardant is 98 wt% to 100 wt%.
Aspect 7: the fiber of any of aspects 1-6, wherein the block polyestercarbonate-polysiloxane comprises 70 mol% to 90 mol% resorcinol ester units, 5 mol% to 15 mol% carbonate units wherein R is based on the total moles of carbonate and ester units1Is 1, 3-phenylene and 5 mol% to 15 mol% of carbonate units in which R is1Is that
Figure BDA0002675963860000151
And further comprises from 0.5 wt% to 2 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane.
Aspect 8: the fiber of any of aspects 1-7, wherein the composition comprises 0-1ppm by weight of a colorant.
Aspect 9: a method of forming a fiber, the method comprising: melt spinning the composition to form a fiber; wherein the composition comprises 90 wt% to 98 wt%, based on the total weight of the composition, of a block polyestercarbonate-polysiloxane comprising polyester blocks comprising resorcinol ester units having the following structure:
Figure BDA0002675963860000152
polycarbonate blocks comprising carbonate units having the structure
Figure BDA0002675963860000161
Wherein R is1At least 60% of the total number of groups are aromatic divalent groups, and polysiloxane blocks containing dimethylsiloxane units; wherein the block polyestercarbonate-polysiloxane comprises from 30 mol% to 90 mol% resorcinol ester units, from 5 mol% to 35 mol% carbonate units wherein R is based on the total moles of carbonate and ester units1Is 1, 3-phenylene and 5 mol% to 35 mol% of carbonate units in which R is1Is that
Figure BDA0002675963860000162
And further comprising 0.2 wt% to 4 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane; and 2 wt% to 10 wt% of a flame retardant; wherein the fibers have an equivalent circular diameter of 10-60 microns.
Aspect 10: the method of aspect 9, wherein the melt spinning is characterized by a draw ratio of 280-550 and an apparent shear rate of 170-1700s-1And a mechanical draw ratio of 0.95 to 1.2.
Aspect 11: an article comprising the fiber of any of aspects 1-8.
Aspect 12: the article of aspect 11, wherein the article comprises a woven fabric comprising the fiber.
Aspect 13: the article of aspect 11, wherein the article comprises a knitted fabric comprising the fiber.
Aspect 14: the article of aspect 11, wherein the article comprises a nonwoven fabric comprising the fibers.
All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Each range disclosed herein constitutes a disclosure of any point or subrange within the disclosed range.
The invention is further illustrated by the following non-limiting examples.
Examples
The materials used in these examples are summarized in table 1.
TABLE 1
Figure BDA0002675963860000171
Figure BDA0002675963860000181
The compositions are summarized in table 2, wherein the amounts of the components are expressed in weight percent based on the total weight of the composition. Each composition was prepared by dry blending all the components and then the resulting mixture was added to the feed throat of a twin screw extruder having a working zone temperature range of 230-300 ℃. The extrudate is granulated after cooling in water.
TABLE 2
Example 1 Example 2 Comparative example 1 Comparative example 2
PEC-Si 93.44 93.44 49.97 87.95
PEC 0.00 0.00 49.97 0.00
OPE 6.50 6.50 0.00 0.00
BrPC 0.00 0.00 0.00 11.99
TBPDP 0.06 0.06 0.06 0.06
SV36 0.00 0.00035 0.00 0.00
PB60 0.00 0.00044 0.00 0.00
The pellets are dried at 80-120 c for 6-12 hours before being fed to the hopper of the melt spinning apparatus. Melt spinning is carried out on a melt spinning apparatus schematically illustrated in the figure. In this figure, a melt spinning apparatus 1 includes an extruder 5 in which dried pellets are converted into a melt, a melt pump 10 that delivers the melt into a spinning pack 15, where the melt is filtered and then passed to a spinneret (spinneret)20, in which a plurality of fibers are formed from the filtered melt. The fibers are immediately conveyed to a quench zone 30 where the fibers are air cooled and solidified. The cooled fiber then enters a spin finish section 40 where a spin finish can be applied to the surface of the fiber. The fiber then traverses a series of godet pairs including a first godet 50, a second godet 60, and a third godet 70, where the fiber is drawn (drawn). The fibers then enter the winder section 80 where the contact roller 90 helps form a wrapped fiber 100 around one of the two wound cores 110.
In these experiments, the melt pump was at 10cm3Speed per revolution. The temperature of the extruder and melt pump was 280-. A 144-hole unit spinneret was used. The spinneret holes (nozzles) are all circular, and the diameter of the spinneret holes (nozzles) is within the range of 0.4-0.8 mm according to the experimental variation. The aspect ratio of each spinneret was 4: 1. A 325 U.S. mesh (44 micron open) screen filter was used in the spin pack assembly to filter the composition melt. After the fibers leave the nozzle, they pass throughIt was solidified by air quenching at ambient temperature (about 23 ℃). The individual filaments are combined to form a multifilament thread (multi-filament thread) and then a spin finish (LUROL from Goulston)TMAcrylamide copolymer in an oil-in-water emulsion obtained from PS-11744) was applied to the multifilament yarn before it was brought into contact with the first godet roll. The draw ratio ranges from 140 for a 16 denier per fiber (dpf) experiment to 2200 for a 2dpf experiment. The apparent shear rate ranged from 43 for 2dpf experiments to 3420 for 16dpf experiments. The mechanical stretching ratio is 0.95-1.2.
For the composition of example 1, the optimum fiber production and the stretch ratios of 280-550 (preferably 350-450), 170-1700s-1(preferably 275--1) The apparent shear rate of (a), a mechanical draw ratio of from 0.95 to 1.2, preferably from 0.98 to 1.1. When the draw ratio is significantly less than 280, the produced fibers do not exhibit uniform diameters, and the productivity of the process is too low to be commercially practical. At draw ratios significantly greater than 550, mechanical breakage of fibers from some of the 144 nozzles was observed, resulting in wire breakage. At a time significantly less than 170s-1At apparent shear rates of (a), the resulting fibers do not have a uniform diameter. At a temperature significantly greater than 1700s-1At apparent shear rates of (a), melt fracture leading to wire breakage was observed. At mechanical draw ratios significantly less than 0.95, frequent yarn breaks on the godet rolls were observed. At mechanical draw ratios significantly greater than 1.2, the threads on the godet roll develop fuzz (fluff) due to filament breakage.
For the composition of example 2, the melt spinning process was acceptable, but not as advantageous as the composition of example 1. Specifically, the number of disconnections per unit time of the composition of example 2 was about three times greater than that of the composition of example 1. For the composition of example 2, most of the yarn breakage occurred between the spinneret and the first godet roll.
For the composition of comparative example 1, the melt spinning process was not stable throughout the process space (process space) studied. Specifically, although fibers can be extruded, they cannot be drawn without unacceptable fiber breakage.
For the composition of comparative example 2, the melt spinning process had a low fiber yield. Fiber breaks occur on average within three to ten minutes. The fibers are capable of being produced and drawn, but the rate of fiber breakage is unacceptable.
The hot air shrinkage was determined as follows. A length of fiber (total length 90 meters, 1 meter per turn) was collected. This set is called a strand (skein) and is made using denier wheels. The strand is held on a hook and its length L is measured in millimeters0Wherein each filament has a basis weight of less than 0.1 g/denier, and the strand is twisted at a set temperature greater than the glass transition temperature (T) of the compositiong) The plates were placed in a convection oven at 20 ℃ lower for 20 minutes. The strands were removed from the convection oven and cooled to ambient temperature. Its length L1Measurements were made in millimeters. The hot air shrinkage, expressed in percent, was calculated as 100 × (L)0-L1)/L0. For the composition of example 1, the hot air shrinkage was 1.5%.

Claims (14)

1. A copolymer fiber:
wherein the multipolymer fiber comprises a composition comprising, based on the total weight of the composition:
from 90 wt% to 98 wt% of a block polyestercarbonate-polysiloxane comprising:
polyester blocks containing resorcinol ester units having the structure
Figure FDA0002675963850000011
Polycarbonate blocks comprising carbonate units having the structure
Figure FDA0002675963850000012
Wherein R is1At least 60% of the total number of groups are aromatic divalent groups, and
polysiloxanes containing dimethylsiloxane unitsBlocking; wherein the block polyestercarbonate-polysiloxane comprises from 30 mol% to 90 mol% resorcinol ester units, from 5 mol% to 35mol carbonate units wherein R is based on the total moles of carbonate units and ester units1Is 1, 3-phenylene, and from 5 mol% to 35 mol% of carbonate units in which R is1Is that
Figure FDA0002675963850000013
And is
Further comprising 0.2 wt% to 4 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane; and
2-10 wt% of a flame retardant;
wherein the fibers have an equivalent circular diameter of 10-60 microns.
2. The fiber of claim 1, wherein the block polyestercarbonate-polysiloxane comprises 0.5 wt% to 2 wt% dimethylsiloxane units.
3. The fiber of claim 1 or 2, wherein the flame retardant comprises an organophosphate ester.
4. The fiber of claim 3, wherein the organophosphate ester comprises an oligomeric phosphate ester.
5. The fiber of any of claims 1-4, wherein the composition comprises 91 wt% to 96 wt% of the block polyestercarbonate-polysiloxane and 4 wt% to 9 wt% of a flame retardant, based on the total weight of the composition.
6. The fiber of any of claims 1-5, wherein the total amount of the block polyestercarbonate-polysiloxane and flame retardant is 98 wt% to 100 wt%.
7. The fiber of any one of claims 1-6, wherein the total is based on carbonate units and ester units(ii) moles, said block polyestercarbonate-polysiloxane comprising 70 mol% to 90 mol% resorcinol ester units, 5 mol% to 15 mol% carbonate units wherein R is1Is 1, 3-phenylene, and from 5 mol% to 15 mol% of carbonate units in which R is1Is that
Figure FDA0002675963850000021
And is
Further comprising 0.5 wt% to 2 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane.
8. The fiber of any of claims 1-6, wherein the composition comprises 0-1 parts per million by weight of a colorant.
9. A method of forming a fiber, the method comprising:
melt spinning the composition to form a fiber;
wherein the composition comprises, based on the total weight of the composition:
from 90 wt% to 98 wt% of a block polyestercarbonate-polysiloxane comprising:
polyester blocks containing resorcinol ester units having the structure
Figure FDA0002675963850000031
Polycarbonate blocks comprising carbonate units having the structure
Figure FDA0002675963850000032
Wherein R is1At least 60% of the total number of groups are aromatic divalent groups, and
a polysiloxane block comprising dimethylsiloxane units; wherein the block polyestercarbonate-polysiloxane comprises 30 mol% based on the total moles of carbonate units and ester units-90 mol% resorcinol ester units, 5 mol% to 35 mol% carbonate units wherein R is1Is 1, 3-phenylene, and from 5 mol% to 35 mol% of carbonate units in which R is1Is that
Figure FDA0002675963850000033
And is
Further comprising 0.2 to 4 wt% of dimethylsiloxane units, based on the weight of the block polyestercarbonate-polysiloxane; and
2-10 wt% of a flame retardant; and
wherein the fibers have an equivalent circular diameter of 10-60 microns.
10. The process of claim 9 wherein the melt spinning is characterized by a draw ratio of 280-550 and an apparent shear rate of 170-1700s-1And a mechanical draw ratio of 0.95 to 1.2.
11. An article comprising the fiber of any of claims 1-8.
12. The article of claim 11, wherein the article comprises a woven fabric comprising the fibers.
13. The article of claim 11, wherein the article comprises a knit fabric comprising the fiber.
14. The article of claim 11, wherein the article comprises a nonwoven fabric comprising the fibers.
CN201980018520.6A 2018-04-30 2019-04-22 Copolymer fibers and related methods and articles Pending CN111836844A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US201862664419P 2018-04-30 2018-04-30
US62/664,419 2018-04-30
EP18197296.9A EP3564291A1 (en) 2018-04-30 2018-09-27 Copolymer fiber and associated method and article
EP18197296.9 2018-09-27
PCT/US2019/028458 WO2019212783A1 (en) 2018-04-30 2019-04-22 Copolymer fiber and associated method and article

Publications (1)

Publication Number Publication Date
CN111836844A true CN111836844A (en) 2020-10-27

Family

ID=63720502

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980018520.6A Pending CN111836844A (en) 2018-04-30 2019-04-22 Copolymer fibers and related methods and articles

Country Status (4)

Country Link
US (1) US20210054144A1 (en)
EP (1) EP3564291A1 (en)
CN (1) CN111836844A (en)
WO (1) WO2019212783A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101528805A (en) * 2006-08-07 2009-09-09 沙伯基础创新塑料知识产权有限公司 Polysiloxane copolymers,thermoplastic composition, and articles formed therefrom
WO2016196427A1 (en) * 2015-05-29 2016-12-08 Sabic Global Technologies B.V. Method of making a curvilinear multilayer article and the articles made therefrom
CN107206735A (en) * 2015-02-04 2017-09-26 沙特基础工业全球技术有限公司 Strengthen thermoplastic article, the composition for article of manufacture, manufacture method and the product formed by it

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6015510A (en) 1996-08-29 2000-01-18 E. I. Du Pont De Nemours And Company Polymer flame retardant
US6025419A (en) 1997-04-07 2000-02-15 E. I. Du Pont De Nemours And Company Flame retardant resin compositions
US7780903B2 (en) * 2005-06-01 2010-08-24 Kimberly-Clark Worldwide, Inc. Method of making fibers and nonwovens with improved properties
EP2173787B1 (en) * 2007-07-26 2019-06-12 SABIC Global Technologies B.V. Crystallizable polyetherimides, method of manufacture, and articles derived therefrom
US20130260088A1 (en) 2012-03-30 2013-10-03 Sabic Innovative Plastics Ip B.V. Honeycomb paper
WO2016154519A1 (en) * 2015-03-25 2016-09-29 Sabic Global Technologies B.V. Poly(arylene sulfide) blend and articles made therefrom
US20180371655A1 (en) * 2015-12-21 2018-12-27 Sabic Global Technologies B.V. Flame resistant polycarbonate composites for semi-structural panels

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101528805A (en) * 2006-08-07 2009-09-09 沙伯基础创新塑料知识产权有限公司 Polysiloxane copolymers,thermoplastic composition, and articles formed therefrom
CN107206735A (en) * 2015-02-04 2017-09-26 沙特基础工业全球技术有限公司 Strengthen thermoplastic article, the composition for article of manufacture, manufacture method and the product formed by it
WO2016196427A1 (en) * 2015-05-29 2016-12-08 Sabic Global Technologies B.V. Method of making a curvilinear multilayer article and the articles made therefrom

Also Published As

Publication number Publication date
US20210054144A1 (en) 2021-02-25
WO2019212783A1 (en) 2019-11-07
EP3564291A1 (en) 2019-11-06

Similar Documents

Publication Publication Date Title
CN102517684B (en) Production process for flame retardant polyester staple fibre
US9267221B2 (en) Phosphonate flame-retardant polyester artificial hair and method of preparing same
PT1812628E (en) Melt-spun multifilament polypropylen yarn formation processes and yarns formed therefrom
CN101812737B (en) Method for producing flame-retardant terylene BCF filaments and application of obtained flame-retardant terylene BCF filaments in carpet weaving
KR20070113232A (en) Process for producing polyphenylene sulfide filament yarns
JP7554392B2 (en) Polyphenylene ether melt spun fiber and its manufacturing method, and paper and fabric
WO2020238687A1 (en) Method for preparing high-strength flame-retardant dacron industrial yarn
KR101865394B1 (en) A manufacturing method of polyester yarn
CN112575447A (en) Processing technology of novel flame-retardant polypropylene spun-bonded non-woven fabric
KR101646563B1 (en) Core-sheath type polyester composite fiber having good flame-retardance and Manufacturing method thereof
KR101992445B1 (en) Process For Producing Polyphenylene Sulfide Filament Fibers And Fibers Therefrom
CN111836844A (en) Copolymer fibers and related methods and articles
CN105273182A (en) Preparation method of flame-retarding nylon 6 and uses thereof
WO2020238688A1 (en) Preparation method for high-modulus, low-shrinkage and flame retardant polyester industrial filament
CN109477248B (en) Polyolefin fiber and method for producing same
KR100663254B1 (en) Process for preparing polyethylene terephthalate bulky continuous filament for carpet
CN107541805B (en) Graphene in-situ polymerization modified polyamide 6 pre-oriented yarn and preparation method thereof
CN115704116B (en) Method for manufacturing aromatic polysulfonamide fiber
CN114514260B (en) Polyphenylene ether melt-extruded molded article and method for producing polyphenylene ether melt-extruded molded article
KR101942300B1 (en) Eco-friendly flame retardant polyethylene multi-filament fiber and manufacturing method thereof
JP2014001467A (en) Method for producing flame retardant polyester fiber
RU2602883C2 (en) Low-pill polyester fibre
WO2020238686A1 (en) Preparation method for low-shrinkage flame-retardant polyester industrial yarns
CN107502972B (en) Graphene in-situ polymerization modified polyamide 6 fully drawn yarn and preparation method thereof
JP2020020053A (en) Polyether sulfone fiber, method for producing the same, and non-woven fabric and paper comprising the fiber

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20210708

Address after: Holland city Aupu zoom Bergen

Applicant after: High tech special engineering plastics Global Technology Co.,Ltd.

Address before: Holland city Aupu zoom Bergen

Applicant before: SABIC GLOBAL TECHNOLOGIES B.V.

TA01 Transfer of patent application right
RJ01 Rejection of invention patent application after publication

Application publication date: 20201027

RJ01 Rejection of invention patent application after publication